Metal coordination compound, luminescence device and display apparatus

ABSTRACT

An electroluminescence device having a layer containing a specific metal coordination compound is provided. The metal coordination compound is represented by formula (1) below: 
     ML m L′ n   (1), 
     wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure MLm is represented by formula (2) shown below and a partial structure ML′ n  is represented by formula (3) or (4) shown below:  
                 
 
     The metal coordination compound of the formula (1) is characterized by having at least one aromatic substituent for at least one of CyN1, CyN2, CyC1 and CyC2. The metal coordination compound having the aromatic substituent is effective in providing high-efficiency luminescence, long-term high luminance, and less deterioration by current passing.

FIELD OF THE INVENTION AND RELATED ART

[0001] The present invention relates to a luminescence device, a displayapparatus and a metal coordination compound therefor. More specifically,the present invention relates to a luminescence device employing anorganic metal coordination compound having a formula (1) appearinghereinafter as a luminescence material so as to allow stableluminescence efficiency, a display apparatus including the luminescencedevice and the metal coordination compound adapted for use in theluminescence device.

[0002] An organic electroluminescence (EL) device has been extensivelystudied as a luminescence device with a high responsiveness and highefficiency.

[0003] The organic EL device generally has a sectional structure asshown in FIG. 1A or 1B (e.g., as described in “Macromol. Symp.”, 125,pp. 1-48 (1997)).

[0004] Referring to the figures, the EL device generally has a structureincluding a transparent substrate 15, a transparent electrode 14disposed on the transparent substrate 15, a metal electrode 11 disposedopposite to the transparent electrode 14, and a plurality of organic(compound) layers disposed between the transparent electrode 14 and themetal electrode 11.

[0005] Referring to FIG. 1, the EL device in this embodiment has twoorganic layers including a luminescence layer 12 and a hole transportlayer 13.

[0006] The transparent electrode 14 may be formed of a film of ITO(indium tin oxide) having a larger work function to ensure a good holeinjection performance into the hole transport layer. On the other hand,the metal electrode 11 may be formed of a layer of aluminum, magnesium,alloys thereof, etc., having a smaller work function to ensure a goodelectron injection performance into the organic layer(s).

[0007] These (transparent and metal) electrodes 14 and 11 may be formedin a thickness of 50-200 nm.

[0008] The luminescence layer 12 may be formed of, e.g., aluminumquinolinol complex (representative example thereof may include Alq3described hereinafter) having an electron transporting characteristicand a luminescent characteristic. The hole transport layer 13 may beformed of, e.g., triphenyldiamine derivative (representative examplethereof may include α-NPD described hereinafter) having an electrondonating characteristic.

[0009] The above-described EL device exhibits a rectificationcharacteristic, so that when an electric field is applied between themetal electrode 11 as a cathode and the transparent electrode 14 as ananode, electrons are injected from the metal electrode 11 into theluminescence layer 12 and holes are injected from the transparentelectrodes 14.

[0010] The thus-injected holes and electrons are recombined within theluminescence layer 12 to produce excitons, thus causing luminescence. Atthat time, the hole transport layer 13 functions as an electron-blockinglayer to increase a recombination efficiency at the boundary between theluminescence layer 12 and the hole transport layer 13, thus enhancing aluminescence efficiency.

[0011] Referring to FIG. 1B, in addition to the layers shown in FIG. 1A,an electron transport layer 16 is disposed between the metal electrode11 and the luminescence layer 12, whereby an effective carrier blockingperformance can be ensured by separating functions of luminescence,electron transport and hole transport, thus allowing effectiveluminescence.

[0012] The electron transport layer 16 may be formed of, e.g.,oxadiazole derivatives.

[0013] In ordinary organic EL devices, fluorescence caused during atransition of luminescent center molecule from a singlet excited stateto a ground state is used as luminescence.

[0014] On the other hand, not the above fluorescence (luminescence) viasinglet exciton, phosphorescence (luminescence) via triplet exciton hasbeen studied for use in organic EL device as described in, e.g.,“Improved energy transfer in electrophosphorescent device” (D. F.O'Brien et al., Applied Physics Letters, Vol. 74, No. 3, pp. 442-444(1999)) and “Very high-efficiency green organic light-emitting devicesbased on electrophosphorescence” (M. A. Baldo et al., Applied PhysicsLetters, Vol. 75, No. 1, pp. 4-6 (1999)).

[0015] The EL devices shown in these documents may generally have asectional structure shown in FIG. 1C.

[0016] Referring to FIG. 1C, four organic layers including a holetransfer layer 13, a luminescence layer 12, an excitondiffusion-prevention layer 17, and an electron transport layer 16 aresuccessively formed in this order on the transparent electrode (anode)14.

[0017] In the above documents, higher efficiencies have been achieved byusing four organic layers including a hole transport layer 13 of α-NPD(shown below), an electron transport layer 16 of Alq3 (shown below), anexciton diffusion-prevention layer 17 of BPC (shown below), and aluminescence layer 12 of a mixture of CPB (shown below) as a hostmaterial with Ir(ppy)₃ (shown below) or PtOEP (shown below) as a guestphosphorescence material doped into CBP at a concentration of ca. 6 wt.%.

[0018] Alq3: tris(8-hydroxyquinoline) aluminum (aluminum-quinolinolcomplex),

[0019] α-NPD:N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4,4′-diamine(4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl),

[0020] CBP: 4,4′-N,N′-dicarbazole-biphenyl,

[0021] BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline,

[0022] Ir(ppy)₃: fac tris(2-phenylpyridine)iridium(iridium-phenylpyridine complex), and

[0023] PtEOP: 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(platinum-octaethyl porphine complex).

[0024] The phosphorescence (luminescence) material used in theluminescence layer 12 has attracted notice. This is because thephosphorescence material is expected to provide a higher luminescenceefficiency in principle.

[0025] More specifically, in the case of the phosphorescence material,excitons produced by recombination of carriers comprise singlet excitonsand triplet excitons presented in a ratio of 1:3. For this reason, whenfluorescence caused during the transition from the singlet excited stateto the ground state is utilized, a resultant luminescence efficiency is25% (as upper limit) based on all the produced excitons in principle.

[0026] On the other hand, in the case of utilizing phosphorescencecaused during transition from the triplet excited state, a resultantluminescence efficiency is expected to be at least three times that ofthe case of fluorescence in principle. In addition thereto, ifintersystem crossing from the singlet excited state (higher energylevel) to the triplet excited state is taken into consideration, theluminescence efficiency of phosphorescence can be expected to be 100%(four times that of fluorescence) in principle.

[0027] The use of phosphorescence based on transition from the tripletexcited state has also been proposed in, e.g., Japanese Laid-Open PatentApplication (JP-A) 11-329739, JP-A 11-256148 and JP-A 8-319482.

[0028] However, the above-mentioned organic EL devices utilizingphosphorescence have accompanied with a problem of luminescentdeterioration particularly in an energized state.

[0029] The reason for luminescent deterioration has not been clarifiedas yet but may be attributable to such a phenomenon that the life oftriplet exciton is generally longer than that of singlet exciton by atleast three digits, so that molecule is placed in a higher-energy statefor a long period to cause reaction with ambient substance, formation ofexciplex or excimer, change in minute molecular structure, structuralchange of ambient substance, etc.

[0030] Accordingly, the (electro)phosphorescence EL device is expectedto provide a higher luminescence efficiency as described above, whilethe EL device is required to suppress or minimize the luminescentdeterioration in energized state. Further, a luminescence centermaterial for the EL device is required to allow high-efficiencyluminescence and exhibit a good stability.

SUMMARY OF THE INVENTION

[0031] An object of the present invention is to provide a luminescencedevice capable of providing a high-efficiency luminescent state at ahigh brightness (or luminance) for a long period while minimizing thedeterioration in luminescence in energized state.

[0032] Another object of the present invention is to provide a displayapparatus including the luminescence device.

[0033] A further object of the present invention is to provide a metalcoordination compound as a luminescence center material suitable for anorganic layer for the luminescence device.

[0034] According to the present invention, there is provided a metalcoordination compound (metal complex), particularly an iridium complex,characterized by having at least one aromatic substituent. Morespecifically, there is provided a metal coordination compoundrepresented by formula (1) below:

ML_(m)L′_(n)  (1),

[0035] wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ aremutually different bidentate ligands; m is 1, 2 or 3 and n is 0, 1 or 2with the proviso that m+n is 2 or 3; a partial structure MLm isrepresented by formula (2) shown below and a partial structure ML′_(n)is represented by formula (3) or (4) shown below:

[0036] wherein CyN1 and CyN2 are each cyclic group capable of having asubstituent, including a nitrogen atom and bonded to the metal atom Mvia the nitrogen atom; CyC1 and CyC2 are each cyclic group capable ofhaving a substituent, including a carbon atom and bonded to the metalatom M via the carbon atom with the proviso that the cyclic group CyN1and the cyclic group CyC1 are bonded to each other via a covalent bondand the cyclic group CyN2 and the cyclic group CyC2 are bonded to eachother via a covalent bond;

[0037] the optional substituent of the cyclic groups is selected from ahalogen atom, cyano group, a nitro group, a trialkylsilyl group of whichthe alkyl groups are independently a linear or branched alkyl grouphaving 1 to 8 carbon atoms, a linear or branched alkyl group having 1 to20 carbon atoms of which the alkyl group can include one ornon-neighboring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl groupcan include a hydrogen atom that can be optionally replaced with afluorine atom; or an aromatic group capable of having a substituentwhich is selected from an aromatic group capable of having a substituent(that is a halogen atom, a cyano atom, a nitro atom, a linear orbranched alkyl group having 1 to 20 carbon atoms of which the alkylgroup can include one or non-neighboring two or more methylene groupsthat can be replaced with —O—, —S—, —CO—, —CO— O—, —O—CO—, —CH═CH— or—C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom), a halogen atom, a cyano atom,a nitro atom, and a linear or branched alkyl group having 1 to 20 carbonatoms (of which the alkyl group can include one or non-neighboring twoor more methylene groups that can be replaced with —O—, S—, —CO—,—CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include ahydrogen atom that can be optionally replaced with a fluorine atom);

[0038] E and G are independently a linear or branched alkyl group having1 to 20 carbon atoms of which the alkyl group can include a hydrogenatom that can be optionally replaced with a fluorine atom, or anaromatic group capable of having a substituent (that is a halogen atom,a cyano atom, a nitro atom, a trialkylsilyl group of which the alkylgroups are independently a linear or branched alkyl group having 1-8carbon atoms, a linear or branched alkyl group having 1 to 20 carbonatoms of which the alkyl group can include one or non-neighboring two ormore methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—,—O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogenatom that can be optionally replaced with a fluorine atom; and

[0039] the cyclic groups CyN1, CyN2, CyC1 and CyC2 have at least onearomatic substituent capable of having a substituent which is selectedfrom an aromatic group capable of having a substituent (that is ahalogen atom, a cyano atom, a nitro atom, a linear or branched alkylgroup having 1 to 20 carbon atoms of which the alkyl group can includeone or non-neighboring two or more methylene groups that can be replacedwith —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C—C—, and the alkylgroup can include a hydrogen atom that can be optionally replaced with afluorine atom), a halogen atom, a cyano atom, a nitro atom, a linear orbranched alkyl group having 1 to 20 carbon atoms of which the alkylgroup can include one or non-neighboring two or more methylene groupsthat can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or—C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom).

[0040] In the formula (1), M may preferably be Ir as described above,and n may preferably be 0.

[0041] In the formula (2), CyN1 and CyC1 may preferably be any one ofthe following combinations: CyN1 CyC1 pyridyl naphthyl pyridyl thienylpyridyl benzothienyl

[0042] The present invention also provides an electroluminescencedevice, comprising: a pair of electrodes disposed on a substrate, and aluminescence unit comprising at least one organic compound disposedbetween the electrodes, wherein the organic compound comprises a metalcoordination compound represented by the above-mentioned formula (1).

[0043] In the electroluminescence device, a voltage is applied betweenthe electrodes to emit light.

[0044] In a preferred embodiment of the electroluminescence device, avoltage is applied between the electrodes to emit phosphorescence.

[0045] The present invention further provides a picture displayapparatus, comprising an electroluminescence device described above anda means for supplying electric signals to the electroluminescencedevice.

[0046] These and other objects, features and advantages of the presentinvention will become more apparent upon a consideration of thefollowing description of the preferred embodiments of the presentinvention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0047]FIGS. 1A, 1B and 1C illustrate embodiments of the luminescencedevice according to the present invention, respectively.

[0048]FIG. 2 schematically illustrates a panel structure including an ELdevice and drive means.

[0049]FIGS. 3A, 3B and 3C show device performances of a luminescencedevice used in Example 9 appearing hereinafter, wherein FIG. 3A shows anelectric field strength-current density curve, FIG. 3B shows an electricfield strength-luminance curve, and FIG. 3C shows a luminescencespectrum under application of a voltage of 10 volts.

DETAILED DESCRIPTION OF THE INVENTION

[0050] In the case where the luminescence layer comprises a hostmaterial having a carrier-transporting function and a phosphorescentguest material, a process of phosphorescence via triplet excitons mayinclude unit processes as follows:

[0051] 1. transportation of electrons and holes within a luminescencelayer,

[0052] 2. formation of host excitons,

[0053] 3. excitation energy transfer between host molecules,

[0054] 4. excitation energy transfer from the host to the guest,

[0055] 5. formation of guest triplet excitons, and

[0056] 6. transition of the guest triplet excitons to the ground stateand phosphorescence.

[0057] Desirable energy transfer in each unit process and luminescenceare caused in competition with various energy deactivation processes.

[0058] Needless to say, a luminescence efficiency of an organicluminescence device is increased by increasing the luminescence quantumyield of a luminescence center material. In addition thereto, anefficient energy transfer between host material molecules and/or betweenhost material molecule and guest material molecule is also an importantfactor.

[0059] Further, the above-described luminescent deterioration inenergized state may presumably relate to the luminescent center materialper se or an environmental change thereof by its ambient molecularstructure.

[0060] For this reason, our research group has extensively investigatedan effect of use of the metal coordination compound of formula (1) asthe luminescent center material and as a result, has found that themetal coordination compound of formula (1) allows a high-efficiencyluminescence with a high brightness (luminance) for a long period, andless deterioration in energized state.

[0061] The metal coordination compound represented by the above formula(1) according to the present invention causes phosphorescence(luminescence) and its lowest excited state is believed to be an MLT*(metal-to-ligand charge transfer) excited state or π-π* excited state ina triplet state. The phosphorescent emission of light (phosphorescence)is caused at the time of transition from such a state to the groundstate.

[0062] The metal coordination compound of formula (1) according to thepresent invention has been found to provide a higher phosphorescence(quantum) yield of 0.05-0.9 and a shorter phosphorescence life of 1-40μsec, as a result of our luminescence experiment based onphotoluminescence by photo-excitation.

[0063] The shorter phosphorescence life is necessary to provide aresultant EL device with a higher luminescence efficiency. This isbecause the longer phosphorescence life increases molecules placed intheir triplet excited state which is a waiting state forphosphorescence, thus lowering the resultant luminescence efficiencyparticularly at a higher current density. Further, an emissionwavelength can be controlled by changing appropriately substituents R1to T6 and species of aromatic group of the metal coordination compoundof the formula (1).

[0064] Also from these viewpoints, the metal coordination compound offormula (1) according to the present invention is a suitable luminescentmaterial for an EL device with a higher phosphorescence yield and ashorter phosphorescence life.

[0065] Particularly, by providing an aromatic group as a substituent(i.e., aromatic substituent) of the metal coordination compound of theformula (1), the resultant substituent has n-electron system extended tothe outside of the metal coordination compound molecules, thusfacilitating energy transfer from a host material and assistingelectron/hole transport functions to result in an improved carriertransport performance. Further, in the present invention, the metalcoordination compound of the formula (1) may preferably have the cyclicgroup CyN1 and/or CyN2 having pyridine structure, a pyridine derivativewherein one of CH groups is substituted with N atom, and fine-memberedring structures containing nitrogen atom and/or sulfur atom. By thesepartial structures, the resultant metal coordination compound of theformula (1) can be synthesized with a high yield and an excellentstability necessary for the luminescence material.

[0066] In addition, as substantiated in Examples appearing hereinafter,it has been confirmed that the metal coordination compound of theformula (1) also exhibited an excellent stability in a durability testby continuous current passage. This may be attributable to a controlledintermolecular interaction of the metal coordination compound of theformula (1) with the host material by introducing the aromaticsubstituent characterizing the metal coordination compound of thepresent invention into the metal coordination compound thereby to changean intermolecular interaction. As a result, it becomes possible tosuppress formation of exciton associates leading to thermaldeactivation, thus also reducing quenching process to improvephosphorescence yield and device characteristics.

[0067] In the present invention, as the aromatic substituent for themetal coordination compound of the formula (1), it is preferred to usean aromatic group selected from the group consisting of those (sPh tosPe) shown hereinafter.

[0068] In the present invention, the luminescence device may preferablyinclude the organic layer comprising the above-mentioned metalcoordination compound between a pair of oppositely disposed electrodescomprising a transparent electrode (anode) and a metal electrode(cathode) which are supplied with a voltage to cause luminescence, thusconstituting an electric-field luminescence device.

[0069] The luminescence device of the present invention has a layerstructure shown in FIGS. 1A to 1C as specifically described above.

[0070] By the use of the metal coordination compound of formula (1) ofthe present invention, the resultant luminescence device has a highluminescence efficiency as described above.

[0071] The luminescence device according to the present invention may beapplicable to devices required to allow energy saving and highluminance, such as those for display apparatus and illuminationapparatus, a light source for printers, and backlight (unit) for aliquid crystal display apparatus. Specifically, in the case of using theluminescence device of the present invention in the display apparatus,it is possible to provide a flat panel display apparatus capable ofexhibiting an excellent energy saving performance, a high visibility anda good lightweight property. With respect to the light source, itbecomes possible to replace a laser light source of laser beam printercurrently used widely with the luminescence device according to thepresent invention. Further, when the luminescence device of the presentinvention is arranged in independently addressable arrays as an exposuremeans for effecting desired exposure of light to a photosensitive drumfor forming an image, it becomes possible to considerably reducing thevolume (size) of image forming apparatus. With respect to theillumination apparatus and backlight (unit), the resultant apparatus(unit) using the luminescence device of the present invention isexpected to have an energy saving effect.

[0072] For the application to a display, a drive system using athin-film transistor (TFT) drive circuit according to an activematrix-scheme may be used. Hereinbelow, an embodiment of using a deviceof the present invention in combination with an active matrix substrateis briefly described with reference to FIG. 2.

[0073]FIG. 2 illustrates an embodiment of panel structure comprising anEL device and drive means. The panel is provided with a scanning signaldriver, a data signal driver and a current supply source which areconnected to gate selection lines, data signal lines and current supplylines, respectively. At each intersection of the gate selection linesand the data signal lines, a display pixel electrode is disposed. Thescanning signal drive sequentially selects the gate selection lines G1,G2, G3 . . . Gn, and in synchronism herewith, picture signals aresupplied from the data signal driver to display a picture (image).

[0074] By driving a display panel including a luminescence layercomprising a luminescence material of the present invention, it becomespossible to provide a display which exhibits a good picture quality andis stable even for a long period display.

[0075] Some synthetic paths for providing a metal coordination compoundrepresented by the above-mentioned formula (1) are illustrated belowwith reference to an iridium coordination compound (m+n=3) for example:

[0076] Other metal coordination compound (M=Pt, Rh and Pd) can also besynthesized in a similar manner.

[0077] Some specific structural examples of metal coordination compoundsused in the present invention are shown in Tables 1 to Tables 17appearing hereinafter, which are however only representative examplesand are not exhaustive. Ph to sPe for CyN1, CyN2, CyC1, CyC2 andaromatic substituent(s) shown in Tables 1 to 17 represent partialstructures shown below.

CyC1, CyC2

[0078]

TABLE 1 No M m CyN1 CyC1 R1 R2 R3 R4 1 Ir 3 Pr Ph H H sPh H 2 Ir 3 Pr PhH H sNp1 H 3 Ir 3 Pr Ph H H sNp2 H 4 Ir 3 Pr Ph H H sTn1 H 5 Ir 3 Pr PhH H sTn3 H 6 Ir 3 Pr Ph H H sPr H 7 Ir 3 Pr Ph H H sPe H 8 Ir 3 Pr Tn1 HH sPh H 9 Ir 3 Pr Tn1 H H sNp1 H 10 Ir 3 Pr Tn1 H H sNp2 H 11 Ir 3 PrTn1 H H sTn1 H 12 Ir 3 Pr Tn1 H H sTn3 H 13 Ir 3 Pr Tn1 H H sPr H 14 Ir3 Pr Tn1 H H sPe H 15 Ir 3 Pr Tn2 H H sPh H 16 Ir 3 Pr Tn2 H H sNp1 H 17Ir 3 Pr Tn2 H H sNp2 H 18 Ir 3 Pr Tn2 H H sTn1 H 19 Ir 3 Pr Tn2 H H sTn3H 20 Ir 3 Pr Tn2 H H sPr H 21 Ir 3 Pr Tn2 H H sPe H 22 Ir 3 Pr Tn3 H HsPh H 23 Ir 3 Pr Tn3 H H sNp1 H 24 Ir 3 Pr Tn3 H H sNp2 H 25 Ir 3 Pr Tn3H H sTn1 H 26 Ir 3 Pr Tn3 H H sTn3 H 27 Ir 3 Pr Tn3 H H sPr H 28 Ir 3 PrTn3 H H sPe H 29 Ir 3 Pr Tn4 H H sPh H 30 Ir 3 Pr Tn4 H H sNp1 H 31 Ir 3Pr Tn4 H H sNp2 H 32 Ir 3 Pr Tn4 H H sTn1 H 33 Ir 3 Pr Tn4 H H sTn3 H 34Ir 3 Pr Tn4 H H sPr H 35 Ir 3 Pr Tn4 H H sPe H 36 Ir 3 Pr Np1 H H sPh H37 Ir 3 Pr Np1 H H sNp1 H 38 Ir 3 Pr Np1 H H sNp2 H 39 Ir 3 Pr Np1 H HsTn1 H 40 Ir 3 Pr Np1 H H sTn3 H 41 Ir 3 Pr Np1 H H sPr H 42 Ir 3 Pr Np1H H sPe H 43 Ir 3 Pr Np2 H H H sPh 44 Ir 3 Pr Np2 H H sNp1 H 45 Ir 3 PrNp2 H H sNp2 H 46 Ir 3 Pr Np2 H H sTn1 H 47 Ir 3 Pr Np2 H H sTn3 H 48 Ir3 Pr Np2 H H sPr H 49 Ir 3 Pr Np2 H H sPe H 50 Ir 3 Pr Pe H H sPh H 51Ir 3 Pr Pe H H sNp1 H 52 Ir 3 Pr Pe H H sNp2 H

[0079] TABLE 2 No M m CyN1 CyC1 R1 R2 R3 R4 53 Ir 3 Pr Pe H H sTn1 H 54Ir 3 Pr Pe H H sTn3 H 55 Ir 3 Pr Pe H H sPr H 56 Ir 3 Pr Pe H H sPe H 57Ir 3 Pr Cn1 H H sPh H 58 Ir 3 Pr Cn1 H H sNp1 H 59 Ir 3 Pr Cn1 H H sNp2H 60 Ir 3 Pr Cn1 H H sTn1 H 61 Ir 3 Pr Cn1 H H sTn3 H 62 Ir 3 Pr Cn1 H HsPr H 63 Ir 3 Pr Cn1 H H sPe H 64 Ir 3 Pr Cn2 H H sPh H 65 Ir 3 Pr Cn2 HH sNp1 H 66 Ir 3 Pr Cn2 H H sNp2 H 67 Ir 3 Pr Cn2 H H sTn1 H 68 Ir 3 PrCn2 H H sTn3 H 69 Ir 3 Pr Cn2 H H sPr H 70 Ir 3 Pr Cn2 H H sPe H 71 Ir 3Pr Cz H H sPh H 72 Ir 3 Pr Cz H H sNp1 H 73 Ir 3 Pr Cz H H sNp2 H 74 Ir3 Pr Cz H H sTn1 H 75 Ir 3 Pr Cz H H sTn3 H 76 Ir 3 Pr Cz H H sPr H 77Ir 3 Pr Cz H H sPe H 78 Ir 3 Pd Ph H H sPh H 79 Ir 3 Pd Ph H H sNp1 H 80Ir 3 Pd Ph H H sNp2 H 81 Ir 3 Pd Ph H H sTn1 H 82 Ir 3 Pd Ph H H sTn3 H83 Ir 3 Pd Ph H H sPr H 84 Ir 3 Pd Ph H H sPe H 85 Ir 3 Pd Tn1 H H sPh H86 Ir 3 Pd Tn1 H H sNp1 H 87 Ir 3 Pd Tn1 H H sNp2 H 88 Ir 3 Pd Tn1 H HsTn1 H 89 Ir 3 Pd Tn1 H H sTn3 H 90 Ir 3 Pd Tn1 H H sPr H 91 Ir 3 Pd Tn1H H sPe H 92 Ir 3 Pd Tn2 H H sPh H 93 Ir 3 Pd Tn2 H H sNp1 H 94 Ir 3 PdTn2 H H sNp2 H 95 Ir 3 Pd Tn2 H H sTn1 H 96 Ir 3 Pd Tn2 H H sTn3 H 97 Ir3 Pd Tn2 H H sPr H 98 Ir 3 Pd Tn2 H H sPe H 99 Ir 3 Pd Tn3 H H sPh H 100Ir 3 Pd Tn3 H H sNp1 H 101 Ir 3 Pd Tn3 H H sNp2 H 102 Ir 3 Pd Tn3 H HsTn1 H 103 Ir 3 Pd Tn3 H H sTn3 H 104 Ir 3 Pd Tn3 H H sPr H

[0080] TABLE 3 No M m CyN1 CyC1 R1 R2 R3 R4 105 Ir 3 Pd Tn3 H H sPe H106 Ir 3 Pd Tn4 H H sPh H 107 Ir 3 Pd Tn4 H H sNp1 H 108 Ir 3 Pd Tn4 H HsNp2 H 109 Ir 3 Pd Tn4 H H sTn1 H 110 Ir 3 Pd Tn4 H H sTn3 H 111 Ir 3 PdTn4 H H sPr H 112 Ir 3 Pd Tn4 H H sPe H 113 Ir 3 Pd Np1 H H sPh H 114 Ir3 Pd Np1 H H sNp1 H 115 Ir 3 Pd Np1 H H sNp2 H 116 Ir 3 Pd Np1 H H sTn1H 117 Ir 3 Pd Np1 H H sTn3 H 118 Ir 3 Pd Np1 H H sPr H 119 Ir 3 Pd Np1 HH sPe H 120 Ir 3 Pd Np2 H H sPh H 121 Ir 3 Pd Np2 H H sNp1 H 122 Ir 3 PdNp2 H H sNp2 H 123 Ir 3 Pd Np2 H H sTn1 H 124 Ir 3 Pd Np2 H H sTn3 H 125Ir 3 Pd Np2 H H sPr H 126 Ir 3 Pd Np2 H H sPe H 127 Ir 3 Pd Pe H H sPh H128 Ir 3 Pd Pe H H sNp1 H 129 Ir 3 Pd Pe H H sNp2 H 130 Ir 3 Pd Pe H HsTn1 H 131 Ir 3 Pd Pe H H sTn3 H 132 Ir 3 Pd Pe H H sPr H 133 Ir 3 Pd PeH H sPe H 134 Ir 3 Pd Cn1 H H sPh H 135 Ir 3 Pd Cn1 H H sNp1 H 136 Ir 3Pd Cn1 H H sNp2 H 137 Ir 3 Pd Cn1 H H sTn1 H 138 Ir 3 Pd Cn1 H H sTn3 H139 Ir 3 Pd Cn1 H H sPr H 140 Ir 3 Pd Cn1 H H sPe H 141 Ir 3 Pd Cn2 H HsPh H 142 Ir 3 Pd Cn2 H H sNp1 H 143 Ir 3 Pd Cn2 H H sNp2 H 144 Ir 3 PdCn2 H H sTn1 H 145 Ir 3 Pd Cn2 H H sTn3 H 146 Ir 3 Pd Cn2 H H sPr H 147Ir 3 Pd Cn2 H H sPe H 148 Ir 3 Pd Cz H H sPh H 149 Ir 3 Pd Cz H H sNp1 H150 Ir 3 Pd Cz H H sNp2 H 151 Ir 3 Pd Cz H H sTn1 H 152 Ir 3 Pd Cz H HsTn3 H 153 Ir 3 Pd Cz H H sPr H 154 Ir 3 Pd Cz H H sPe H 155 Ir 3 Pz PhH H sPh H 156 Ir 3 Pd Ph H H sNp1 H

[0081] TABLE 4 No M m CyN1 CyC1 R1 R2 R3 R4 157 Ir 3 Pd Ph H H sNp2 H158 Ir 3 Pd Ph H H sTn1 H 159 Ir 3 Pd Ph H H sTn3 H 160 Ir 3 Pd Ph H HsPr H 161 Ir 3 Pd Ph H H sPe H 162 Ir 3 Pd Tn1 H H sPh H 163 Ir 3 Pd Tn1H H sNp1 H 164 Ir 3 Pd Tn1 H H sNp2 H 165 Ir 3 Pd Tn1 H H sTn1 H 166 Ir3 Pd Tn1 H H sTn3 H 167 Ir 3 Pd Tn1 H H sPr H 168 Ir 3 Pd Tn1 H H sPe H169 Ir 3 Pd Tn2 H H sPh H 170 Ir 3 Pd Tn2 H H sNp1 H 171 Ir 3 Pd Tn2 H HsNp2 H 172 Ir 3 Pd Tn2 H H sTn1 H 173 Ir 3 Pd Tn2 H H sTn3 H 174 Ir 3 PdTn2 H H sPr H 175 Ir 3 Pd Tn2 H H sPe H 176 Ir 3 Pd Tn3 H H sPh H 177 Ir3 Pd Tn3 H H sNp1 H 178 Ir 3 Pd Tn3 H H sNp2 H 179 Ir 3 Pd Tn3 H H sTn1H 180 Ir 3 Pd Tn3 H H sTn3 H 181 Ir 3 Pd Tn3 H H sPr H 182 Ir 3 Pd Tn3 HH sPe H 183 Ir 3 Pd Tn4 H H sPh H 184 Ir 3 Pd Tn4 H H sNp1 H 185 Ir 3 PdTn4 H H sNp2 H 186 Ir 3 Pd Tn4 H H sTn1 H 187 Ir 3 Pd Tn4 H H sTn3 H 188Ir 3 Pd Tn4 H H sPr H 189 Ir 3 Pd Tn4 H H sPe H 190 Ir 3 Pd Np1 H H sPhH 191 Ir 3 Pd Np1 H H sNp1 H 192 Ir 3 Pd Np1 H H sNp2 H 193 Ir 3 Pd Np1H H sTn1 H 194 Ir 3 Pd Np1 H H sTn3 H 195 Ir 3 Pd Np1 H H sPr H 196 Ir 3Pd Np1 H H sPe H 197 Ir 3 Pd Np2 H H sPh H 198 Ir 3 Pd Np2 H H sNp1 H199 Ir 3 Pd Np2 H H sNp2 H 200 Ir 3 Pd Np2 H H sTn1 H 201 Ir 3 Pd Np2 HH sTn3 H 202 Ir 3 Pd Np2 H H sPr H 203 Ir 3 Pd Np2 H H sPe H 204 Ir 3 PdPe H H sPh H 205 Ir 3 Pd Pe H H sNp1 H 206 Ir 3 Pd Pe H H sNp2 H 207 Ir3 Pd Pe H H sTn1 H 208 Ir 3 Pd Pe H H sTn3 H

[0082] TABLE 5 No M m CyN1 CyC1 R1 R2 R3 R4 209 Ir 3 Pd Pe H H sPr H 210Ir 3 Pd Pe H H sPe H 211 Ir 3 Pd Cn1 H H sPh H 212 Ir 3 Pd Cn1 H H sNp1H 213 Ir 3 Pd Cn1 H H sNp2 H 214 Ir 3 Pd Cn1 H H sTn1 H 215 Ir 3 Pd Cn1H H sTn3 H 216 Ir 3 Pd Cn1 H H sPr H 217 Ir 3 Pd Cn1 H H sPe H 218 Ir 3Pd Cn2 H H sPh H 219 Ir 3 Pd Cn2 H H sNp1 H 220 Ir 3 Pd Cn2 H H sNp2 H221 Ir 3 Pd Cn2 H H sTn1 H 222 Ir 3 Pd Cn2 H H sTn3 H 223 Ir 3 Pd Cn2 HH sPr H 224 Ir 3 Pd Cn2 H H sPe H 225 Ir 3 Pd Cz H H sPh H 226 Ir 3 PdCz H H sNp1 H 227 Ir 3 Pd Cz H H sNp2 H 228 Ir 3 Pd Cz H H sTn1 H 229 Ir3 Pd Cz H H sTn3 H 230 Ir 3 Pd Cz H H sPr H 231 Ir 3 Pd Cz H H sPe H 232Ir 3 Pz Ph H H sPh H 233 Ir 3 Pz Ph H H sNp1 H 234 Ir 3 Pz Ph H H sNp2 H235 Ir 3 Pz Ph H H sTn1 H 236 Ir 3 Pz Ph H H sTn3 H 237 Ir 3 Pz Ph H HsPr H 238 Ir 3 Pz Ph H H sPe H 239 Ir 3 Pz Tn1 H H sPh H 240 Ir 3 Pz Tn1H H sNp1 H 241 Ir 3 Pz Tn1 H H sNp2 H 242 Ir 3 Pz Tn1 H H sTn1 H 243 Ir3 Pz Tn1 H H sTn3 H 244 Ir 3 Pz Tn1 H H sPr H 245 Ir 3 Pz Tn1 H H sPe H246 Ir 3 Pz Tn2 H H sPh H 247 Ir 3 Pz Tn2 H H sNp1 H 248 Ir 3 Pz Tn2 H HsNp2 H 249 Ir 3 Pz Tn2 H H sTn1 H 250 Ir 3 Pz Tn2 H H sTn3 H 251 Ir 3 PzTn2 H H sPr H 252 Ir 3 Pz Tn2 H H sPe H 253 Ir 3 Pz Tn3 H H sPh H 254 Ir3 Pz Tn3 H H sNp1 H 255 Ir 3 Pz Tn3 H H sNp2 H 256 Ir 3 Pz Tn3 H H sTn1H 257 Ir 3 Pz Tn3 H H sTn3 H 258 Ir 3 Pz Tn3 H H sPr H 259 Ir 3 Pz Tn3 HH sPe H 260 Ir 3 Pz Tn4 H H sPh H

[0083] TABLE 6 No M m CyN1 CyC1 R1 R2 R3 R4 261 Ir 3 Pz Tn4 H H sNp1 H262 Ir 3 Pz Tn4 H H sNp2 H 263 Ir 3 Pz Tn4 H H sTn1 H 264 Ir 3 Pz Tn4 HH sTn3 H 265 Ir 3 Pz Tn4 H H sPr H 266 Ir 3 Pz Tn4 H H sPe H 267 Ir 3 PzNp1 H H sPh H 268 Ir 3 Pz Np1 H H sNp1 H 269 Ir 3 Pz Np1 H H sNp2 H 270Ir 3 Pz Np1 H H sTn1 H 271 Ir 3 Pz Np1 H H sTn3 H 272 Ir 3 Pz Np1 H HsPr H 273 Ir 3 Pz Np1 H H sPe H 274 Ir 3 Pz Np2 H H sPh H 275 Ir 3 PzNp2 H H sNp1 H 276 Ir 3 Pz Np2 H H sNp2 H 277 Ir 3 Pz Np2 H H sTn1 H 278Ir 3 Pz Np2 H H sTn3 H 279 Ir 3 Pz Np2 H H sPr H 280 Ir 3 Pz Np2 H H sPeH 281 Ir 3 Pz Pe H H sPh H 282 Ir 3 Pz Pe H H sNp1 H 283 Ir 3 Pz Pe H HsNp2 H 284 Ir 3 Pz Pe H H sTn1 H 285 Ir 3 Pz Pe H H sTn3 H 286 Ir 3 PzPe H H sPr H 287 Ir 3 Pz Pe H H sPe H 288 Ir 3 Pz Cn1 H H sPh H 289 Ir 3Pz Cn1 H H sNp1 H 290 Ir 3 Pz Cn1 H H sNp2 H 291 Ir 3 Pz Cn1 H H sTn1 H292 Ir 3 Pz Cn1 H H sTn3 H 293 Ir 3 Pz Cn1 H H sPr H 294 Ir 3 Pz Cn1 H HsPe H 295 Ir 3 Pz Cn2 H H sPh H 296 Ir 3 Pz Cn2 H H sNp1 H 297 Ir 3 PzCn2 H H sNp2 H 298 Ir 3 Pz Cn2 H H sTn1 H 299 Ir 3 Pz Cn2 H H sTn3 H 300Ir 3 Pz Cn2 H H sPr H 301 Ir 3 Pz Cn2 H H sPe H 302 Ir 3 Pz Cz H H sPh H303 Ir 3 Pz Cz H H sNp1 H 304 Ir 3 Pz Cz H H sNp2 H 305 Ir 3 Pz Cz H HsTn1 H 306 Ir 3 Pz Cz H H sTn3 H 307 Ir 3 Pz Cz H H sPr H 308 Ir 3 Pz CzH H sPe H 309 Ir 3 Py1 Ph H H sPh H 310 Ir 3 Py1 Ph H H sNp1 H 311 Ir 3Py1 Ph H H sTn1 H 312 Ir 3 Py1 Ph H H sTn3 H

[0084] TABLE 7 No M m CyN1 CyC1 R1 R2 R3 R4 313 Ir 3 Py1 Tn1 H H sPh H314 Ir 3 Py1 Tn1 H H sNp1 H 315 Ir 3 Py1 Tn1 H H sTn1 H 316 Ir 3 Py1 Tn1H H sTn3 H 317 Ir 3 Py1 Tn3 H H sPh H 318 Ir 3 Py1 Tn3 H H sNp1 H 319 Ir3 Py1 Tn3 H H sTn1 H 320 Ir 3 Py1 Tn3 H H sTn3 H 321 Ir 3 Py1 Tn4 H HsPh H 322 Ir 3 Py1 Tn4 H H sNp1 H 323 Ir 3 Py1 Tn4 H H sTn1 H 324 Ir 3Py1 Tn4 H H sTn3 H 325 Ir 3 Py1 Np2 H H sPh H 326 Ir 3 Py1 Np2 H H sNp1H 327 Ir 3 Py1 Np2 H H sTn1 H 328 Ir 3 Py1 Np2 H H sTn3 H 329 Ir 3 Py2Ph H H sPh H 330 Ir 3 Py2 Ph H H sNp1 H 331 Ir 3 Py2 Ph H H sTn1 H 332Ir 3 Py2 Ph H H sTn3 H 333 Ir 3 Py2 Tn1 H H sPh H 334 Ir 3 Py2 Tn1 H HsNp1 H 335 Ir 3 Py2 Tn1 H H sTn1 H 336 Ir 3 Py2 Tn1 H H sTn3 H 337 Ir 3Py2 Tn3 H H sPh H 338 Ir 3 Py2 Tn3 H H sNp1 H 339 Ir 3 Py2 Tn3 H H sTn1H 340 Ir 3 Py2 Tn3 H H sTn3 H 341 Ir 3 Py2 Tn4 H H sPh H 342 Ir 3 Py2Tn4 H H sNp1 H 343 Ir 3 Py2 Tn4 H H sTn1 H 344 Ir 3 Py2 Tn4 H H sTn3 H345 Ir 3 Py2 Np2 H H sPh H 346 Ir 3 Py2 Np2 H H sNp1 H 347 Ir 3 Py2 Np2H H sTn1 H 348 Ir 3 Py2 Np2 H H sTn3 H 349 Ir 3 Pr Ph sPh H H H 350 Ir 3Pr Ph sNp2 H H H 351 Ir 3 Pr Ph sTn1 H H H 352 Ir 3 Pr Ph sTn3 H H H 353Ir 3 Pr Tn1 sPh H H H 354 Ir 3 Pr Tn1 sNp2 H H H 355 Ir 3 Pr Tn1 sTn1 HH H 356 Ir 3 Pr Tn1 sTn3 H H H 357 Ir 3 Pr Tn3 sPh H H H 358 Ir 3 Pr Tn3sNp2 H H H 359 Ir 3 Pr Tn3 sTn1 H H H 360 Ir 3 Pr Tn3 sTn3 H H H 361 Ir3 Pr Np2 sPh H H H 362 Ir 3 Pr Np2 sNp2 H H H 363 Ir 3 Pr Np2 sTn1 H H H364 Ir 3 Pr Np2 sTn3 H H H

[0085] TABLE 8 No M m CyN1 CyC1 R1 R2 R3 R4 365 Ir 3 Pz Ph sPh H H H 366Ir 3 Pz Ph sNp2 H H H 367 Ir 3 Pz Ph sTn1 H H H 368 Ir 3 Pz Ph sTn3 H HH 369 Ir 3 Pz Tn1 sPh H H H 370 Ir 3 Pz Tn1 sNp2 H H H 371 Ir 3 Pz Tn1sTn1 H H H 372 Ir 3 Pz Tn1 sTn3 H H H 373 Ir 3 Pz Tn3 sPh H H H 374 Ir 3Pz Tn3 sNp2 H H H 375 Ir 3 Pz Tn3 sTn1 H H H 376 Ir 3 Pz Tn3 sTn3 H H H377 Ir 3 Pz Np2 sPh H H H 378 Ir 3 Pz Np2 sNp2 H H H 379 Ir 3 Pz Np2sTn1 H H H 380 Ir 3 Pz Np2 sTn3 H H H

[0086] TABLE 9 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 381 Ir 3 Pr Ph sPh H HH H —NO2 382 Ir 3 Pr Ph sNp2 H —CH3 H H H 383 Ir 3 Pr Ph sTn1 H H H —CF3H 384 Ir 3 Pr Ph sTn3 H H H H sPh 385 Ir 3 Pr Tn1 sPh H H H —OCH₃ H 386Ir 3 Pr Tn1 sNp2 H H H H sPh 387 Ir 3 Pr Tn1 sTn1 H H H H —CF3 388 Ir 3Pr Tn1 sTn3 H H H H sPh 389 Ir 3 Pr Tn3 sPh H H H —OCH₃ H 390 Ir 3 PrTn3 sNp2 H H H H —OCH₃ 391 Ir 3 Pr Tn3 sTn1 H H H H —OCH₃ 392 Ir 3 PrTn3 sTn3 H H H —OCH₃ H 393 Ir 3 Pr Np2 sPh H H H —OCH₃ H 394 Ir 3 Pr Np2sNp2 H H H H sPh 395 Ir 3 Pr Np2 sTn1 H H H H sPh 396 Ir 3 Pr Np2 sTn3 HH H H —OCH₃ 397 Ir 3 Pz Ph sPh H H —OCH₃ H H 398 Ir 3 Pz Ph sNp2 H H—OCH₃ H H 399 Ir 3 Pz Ph sTn1 H H H H —OCH₃ 400 Ir 3 Pz Ph sTn3 H H H H—OCH₃ 401 Ir 3 Pz Tn1 sPh H —C3H7 H H H 402 Ir 3 Pz Tn1 sNp2 H H H H H403 Ir 3 Pz Tn1 sTn1 H H H H H 404 Ir 3 Pz Tn1 sTn3 H H H H sPh 405 Ir 3Pz Tn3 sPh H H H H —OCH₃ 406 Ir 3 Pz Tn3 sNp2 H H —OCH₃ H H 407 Ir 3 PzTn3 sTn1 H H —OCH₃ H H 408 Ir 3 Pz Tn3 sTn3 H H H H —OCH₃ 409 Ir 3 PzNp2 sPh H H H H —OCH₃ 410 Ir 3 Pz Np2 sNp2 H —C3H7 H H H

[0087] TABLE 10 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 411 Ir 3 Pz Np2 sTn1H H —CF3 H H 412 Ir 3 Pz Np2 sTn3 H H —CF3 H H 413 Ir 3 Ta Ph C4H9 C4H9sPh H OCH3 H 414 Ir 3 Pr Ph sPh H H H H H 415 Ir 3 Pr Ph sNp2 H —CH3 H HH 416 Ir 3 Pr Ph sTn1 H H H H H 417 Ir 3 Pr Ph sTn3 H H H H H 418 Ir 3Pr Tn1 sPh H H H —OCH₃ H 419 Ir 3 Pr Tn1 sNp2 H H H H H 420 Ir 3 Pr Tn1sTn1 H H H H H 421 Ir 3 Pr Tn1 sTn3 H H H H H 422 Ir 3 Pr Tn3 sPh H H H—OCH₃ H 423 Ir 3 Pr Tn3 sNp2 H H H H H 424 Ir 3 Pr Tn3 sTn1 H —NO2 H H H425 Ir 3 Pr Tn3 sTn3 H H H H H 426 Ir 3 Pr Np2 sPh H H H H H 427 Ir 3 PrNp2 sNp2 H H H H H 428 Ir 3 Pr Np2 sTn1 H H H H H 429 Ir 3 Pr Np2 sTn3 HH H H H 430 Ir 3 Pz Ph sPh H H —F H H 431 Ir 3 Pz Ph sNp2 H H H H H 432Ir 3 Pz Ph sTn1 —CN H H H H 433 Ir 3 Pz Ph sTn3 H H H H H 434 Ir 3 PzTn1 sPh H —C3H7 H H H 435 Ir 3 Pz Tn1 sNp2 H H —CH2— H H CH═CH —CH3 436Ir 3 Pz Tn1 sTn1 H H H H H 437 Ir 3 Pz Tn1 sTn3 H H H H H 438 Ir 3 PzTn3 sPh H —SC3H7 H H H 439 Ir 3 Pz Tn3 sNp2 H H H H H 440 Ir 3 Pz Tn3sTn1 H H H H H 441 Ir 3 Pz Tn3 sTn3 H H H H 442 Ir 3 Pz Np2 sPh H H H HH 443 Ir 3 Pz Np2 sNp2 H H H H H 444 Ir 3 Pz Np2 sTn1 H H H H H 445 Ir 3Pz Np2 sTn3 H H H H H

[0088] TABLE 11 No M m n CyN1 CyC1 CyN2 CyC2 R1 R2 R3 R4 R1′ R2′ R3′ R4′446 Ir 2 1 Pr Ph Pr Tn1 sPh H H H sPh H H H 447 Ir 2 1 Pr Ph Pr Tn1 sNp2H H H sNp2 H H H 448 Ir 2 1 Pr Ph Pr Tn1 sTn1 H H H sTn1 H H H 449 Ir 21 Pr Ph Pr Tn1 sTn3 H H H sTn3 H H H 450 Ir 2 1 Pr Tn3 Pr Np2 sPh H H HsPh H H H 451 Ir 2 1 Pr Tn3 Pr Np2 sNp2 H H H sNp2 H H H 452 Ir 2 1 PrTn3 Pr Np2 sTn1 H H H sTn1 H H H 453 Ir 2 1 Pr Tn3 Pr Np2 sTn3 H H HsTn3 H H H

[0089] TABLE 12 No M m n CyN1 CyC1 E G R1 R2 R3 R4 454 Ir Ir 1 Pr Ph—CH3 —CH3 sPh H H H 455 Ir Ir 1 Pr Ph —CH3 —CH3 sNp2 H H H 456 Ir Ir 1Pr Ph —CH3 —CH3 sTn1 H H H 457 Ir Ir 1 Pr Ph —CH3 —CH3 H H sTn3 H 458 IrIr 1 Pr Tn3 —CH3 sPh H H sPh H 459 Ir Ir 1 Pr Tn3 —CH3 sPh H H sNp2 H460 Ir Ir 1 Pr Tn3 —CH3 sPh H H sTn1 H 461 Ir Ir 1 Pr Tn3 —CH3 sPh H HsTn3 H

[0090] TABLE 13 No M m CyN1 CyC1 R1 R2 R3 R4 462 Rh 3 Pr Ph sPh H H H463 Rh 3 Pr Ph sNp2 H H H 464 Rh 3 Pr Ph sTn1 H H H 465 Rh 3 Pr Ph sTn3H H H 466 Rh 3 Pr Tn1 sPh H H H 467 Rh 3 Pr Tn1 sNp2 H H H 468 Rh 3 PrTn1 sTn1 H H H 469 Rh 3 Pr Tn1 sTn3 H H H 470 Rh 3 Pr Tn3 sPh H H H 471Rh 3 Pr Tn3 sNp2 H H H 472 Rh 3 Pr Tn3 sTn1 H H H 473 Rh 3 Pr Tn3 sTn3 HH H 474 Rh 3 Pr Np2 sPh H H H 475 Rh 3 Pr Np2 sNp2 H H H 476 Rh 3 Pr Np2sTn1 H H H 477 Rh 3 Pr Np2 sTn3 H H H

[0091] TABLE 14 No M m CyN1 CyC1 R1 R2 R3 R4 478 Pt 2 Pr Ph sPh H H H479 Pt 2 Pr Ph sNp2 H H H 480 Pt 2 Pr Ph sTn1 H H H 481 Pt 2 Pr Ph sTn3H H H 482 Pt 2 Pr Tn1 sPh H H H 483 Pt 2 Pr Tn1 sNp2 H H H 484 Pt 2 PrTn1 sTn1 H H H 485 Pt 2 Pr Tn1 sTn3 H H H 486 Pt 2 Pr Tn3 sPh H H H 487Pt 2 Pr Tn3 sNp2 H H H 488 Pt 2 Pr Tn3 sTn1 H H H 489 Pt 2 Pr Tn3 sTn3 HH H 490 Pt 2 Pr Np2 sPh H H H 491 Pt 2 Pr Np2 sNp2 H H H 492 Pt 2 Pr Np2sTn1 H H H 493 Pt 2 Pr Np2 sTn3 H H H

[0092] TABLE 15 No M m CyN1 CyC1 R1 R2 R3 R4 494 Pd 2 Pr Ph sPh H H H495 Pd 2 Pr Ph sNp2 H H H 496 Pd 2 Pr Ph sTn1 H H H 497 Pd 2 Pr Ph sTn3H H H 498 Pd 2 Pr Tn1 sPh H H H 499 Pd 2 Pr Tn1 sNp2 H H H 500 Pd 2 PrTn1 sTn1 H H H 501 Pd 2 Pr Tn1 sTn3 H H H 502 Pd 2 Pr Tn3 sPh H H H 503Pd 2 Pr Tn3 sNp2 H H H 504 Pd 2 Pr Tn3 sTn1 H H H 505 Pd 2 Pr Tn3 sTn3 HH H 506 Pd 2 Pr Np2 sPh H H H 507 Pd 2 Pr Np2 sNp2 H H H 508 Pd 2 Pr Np2sTn1 H H H 509 Pd 2 Pr Np2 sTn3 H H H

[0093] TABLE 16 No M m CyN1 CyC1 R1 R2 R3 R4 R5 R6 510 Ir 3 Pr Ph sPe HH H H H 511 Ir 3 Pr Ph sPh H sPh H

H 512 Ir 3 Pr Ph H

sPh H H

513 Ir 3 Pr Np2 sPe H H H H H 514 Ir 3 Pr Np2 H H sTn1 H CH3 H 515 Ir 3Pr Tn1 CH3 H sTn1 H CH3 H 516 Ir 3 Pr Tn1 sPh H sTn1 H sPh H

[0094] TABLE 17 No M m n CyN1 CyC1 R1 R2 R3 R4 E G 517 Ir 2 1 Pr Tn3 H HsPh H CH3 CH3 518 Ir 2 1 Pr Tn1 H H sTn1 H CH3 CH3 519 Ir 2 1 Pr Np2 H HsNp2 H CH3 CH3 520 Ir 3 0 Py1 Ph sPh H H H — — 521 Ir 3 0 Py1 Ph sNp1 HH H — — 522 Ir 3 0 Pr Ph H H H sPh — — 523 Ir 3 0 Pr Ph H sPh H H — —524 Ir 3 0 Pr Tn1 Ph H H H — — 525 Ir 2 1 Py1 Ph sPh H H H CH3 CH3 526Ir 2 1 Py1 Ph sNp1 H H H CH3 CH3 527 Ir 2 1 Pr Ph H H H sPh CH3 CH3 528Ir 2 1 Pr Ph H sPh H H CH3 CH3 529 Ir 2 1 Pr Tn1 Ph H H H CH3 CH3

[0095] Hereinbelow, the present invention will be described morespecifically based on Examples.

EXAMPLES 1-6

[0096] Each of luminescence devices having a layer structure shown inFIG. 1B were prepared in the following manner.

[0097] On a 1.1 mm-thick glass substrate (transparent substrate 15), a100 nm-thick film (transparent electrode 14) of ITO (indium tin oxide)was formed by sputtering, followed by patterning to form a stripeelectrode including 100 lines each having a width of 100 nm and aspacing with an adjacent line of 10 nm (i.e., electrode pitch of 110nm).

[0098] On the ITO-formed substrate, three organic layers and two metalelectrode layers shown below were successively formed by vacuum (vapor)deposition using resistance heating in a vacuum chamber (10⁻⁴ Pa).

[0099] Organic layer 1 (hole transport layer 13) (40 nm): α-NPD

[0100] Organic layer 2 (luminescence layer 12) (30 nm): co-depositedfilm of CBP:metal complex (metal coordination compound shown in Table20) (95:5 by weight)

[0101] Organic layer 3 (electron transport layer 16) (30 nm): Alq3

[0102] Metal electrode layer 1 (metal electrode 11)

[0103] (15 nm): Al—Li alloy (Li=1.8 wt. %) Metal electrode layer 2(metal electrode 11) (100 nm): Al

[0104] The above-deposited metal electrode layers 1 and 2 (Al—Li layerand Al layer) had a stripe electrode pattern including 100 lines eachhaving a width of 100 nm and a spacing of 10 nm (electrode pitch=110 nm)and arranged so that the stripe electrode pattern intersected with thatof the ITO electrode at right angles to form a matrix of pixels eachhaving an effective electrode area of 3 mm² comprising 20 ITO linesbundled together at a lead-out portion and 15 Al (Al—Li) lines bundledtogether at a lead-out portion.

[0105] Each of the thus-prepared luminescence devices was taken out ofthe vacuum chamber and was subjected to a continuous energization(current passage) test in an atmosphere of dry nitrogen gas stream so asto remove device deterioration factors, such as oxygen and moisture(water content).

[0106] The continuous energization test was performed by continuouslyapplying a voltage at a constant current density of 50 mA/cm² to theluminescence device having the ITO (transparent) electrode (as an anode)and the Al (metal) electrode (as a cathode), followed by measurement ofemission luminance (brightness) with time so as to determine a time(luminance half-life) required for decreasing an initial luminance(60-220 cd/m²) to ½ thereof.

[0107] The results are shown in Table 18 appearing hereinafter.

Comparative Example 1

[0108] A comparative luminescence device was prepared and evaluated inthe same manner as in Examples 1-6 except that the Ir complexes (metalcoordination compounds shown in Table 20) was changed toIr-phenylpyrimidine complex (Ir(ppy)₃) shown below.

[0109] The results are also shown in Table 18 below. TABLE 18 Ex. No.Compound No. Luminance half-life (Hr) Ex. 1 3 450 Ex. 2 11 550 Ex. 3 22500 Ex. 4 43 500 Ex. 5 45 600 Ex. 6 385 400 Ex. 7 413 650 Comp.Ex. 1Ir(ppy)₃ 300

[0110] As is apparent from Table 18, compared with the conventionalluminescence device using Ir(ppy)₃, the luminescence devices using themetal coordination compounds of formula (1) according to the presentinvention provide longer luminance half-lives, thus resulting in an ELdevice having a high durability (luminance stability) based on a goodstability of the metal coordination compound of formula (1) of thepresent invention.

EXAMPLE 7

[0111] A color organic EL display apparatus shown in FIG. 2 was preparedin the following manner.

[0112] An active matrix substrate had a planar structure basicallysimilar to a structure described in U.S. Pat. No. 6,114,715.

[0113] Specifically, on a 1.1 mm-thick glass substrate, top state-typeTFTs of polycrystalline silicon were formed in an ordinary manner andthereon, a flattening film was formed with contact holes for electricalconnection with a pixel electrode (anode) at respective source regions,thus preparing an active matrix substrate with a TFT circuit.

[0114] On the active matrix substrate, a 700 nm-thick pixel electrode(anode) of ITO having a larger work function was formed in a prescribedpattern. On the ITO electrode, prescribed organic layers and a 100nm-thick Al electrode (cathode) were successively formed by vacuumdeposition with a hard mask, followed by patterning to form a matrix ofcolor pixels (128×128 pixels).

[0115] The respective organic layers corresponding to three color pixels(red (R) green (G) and blue (B)) were-consisting of the followinglayers.

R Pixel Region

[0116] α-NPD (40 nm)/CBP: Ex. Comp. No. 22 (93:7 by weight) (30 nm)/BCP(20 nm)/Alq 3 (40 nm)

G Pixel Region

[0117] α-NPD (50 nm)/Alq 3 (50 nm)

B Pixel Region

[0118] α-NPD (50 nm)/BCP (20 nm)/Alq 3 (50 nm)

[0119] When the thus-prepared color organic EL display apparatus wasdriven, desired color image data can be displayed stably with good imagequalities.

EXAMPLE 8 Synthesis of Example Compound No. 22

[0120]

[0121] In a 500 ml-three-necked flask, 12.6 g (85.2 mM) of2,5-dichloropyridine, 15.2 g (85.4 mM) of benzothiophene-2-boronic acid,75 ml of toluene, 37.5 ml of ethanol and 75 ml of 2M-sodium carbonateaqueous solution were placed and stirred at room temperature undernitrogen stream, and 3.06 g (2.64 mM) oftetrakis(triphenylphosphine)palladium (0) was added thereto, followed byrefluxing under stirring for 8 hours under nitrogen stream. After thereaction, the reaction mixture was cooled on an ice bath to precipitatea crystal, which was then filtered out and washed with water. To thecrystal, 100 ml of methanol was added and washed under stirring at roomtemperature, followed by filtration to recover the crystal. The crystalwas purified by silica gel column chromatography (eluent: chloroform)and recrystallized from a mixture solvent of chloroform-methanol toobtain 11.8 g (Yield: 56.4%) of 5-chloro-2-(benzo[b]thienyl)pyridine(colorless crystal).

[0122] In a 100 ml-three-necked flask, 4.91 g (20.0 mM) of5-chloro-2-(benzo[b]thienyl)pyridine, 3.66 g (30.0 mM) of phenylboronicacid, 9.58 g (40.0 mM) of tripotassium phosphate hydrate, 3.2 mg (0.020mM) of palladium (II) acetate, 11.9 mg (0.040 mM) of2-ditert-butylphosphinobiphenyl and 60 ml of toluene were placed andrefluxed under stirring for 24 hours at 100° C. under nitrogen stream.After the reaction, the reaction mixture was cooled on an ice bath toprecipitate a crystal, which was then filtered out and washed withwater. To the crystal, 25 ml of methanol was added and washed understirring at room temperature, followed by recovery by filtration. Thecrystal was purified by silica gel column chromatography (eluent:chloroform) and recrystallized from a chloroform-methanol mixturesolvent to obtain 1.17 g (Yield: 20.4%) of2-(benzo[b]thienyl)-5-phenylpyridine (colorless crystal).

[0123] In a 100 ml-four-necked flask, 50 ml of glycerol was placed andheated at 130-140° C. under stirring and bubbling with nitrogen for 2hours. Then, the glycerol was cooled by standing to 100° C., and 1.15 g(4.00 mM) of 2-(benzo[b]thienyl)-5-phenylpyridine and 0.40 g (0.82 mM)of iridium (III) acetylacetonate were added thereto, followed bystirring for 5 hours at 180-235° C. under nitrogen stream. The reactionmixture was cooled to room temperature and poured into 300 ml ofIN-hydrochloric acid to form a precipitate. The precipitate wasrecovered by filtration and washed with water, followed by drying for 5hours at 100° C. under reduced pressure. The resultant precipitate wassilica gel column chromatography (eluent: chloroform) to obtain 0.26 g(Yield: 30.2%) of red powderytris[2-(benzo-[b]thienyl)-5-phenylpyridine-C²,N]iridium (III).

[0124] According to MALDI-TOF MS (matrix-assisted laser desorptionionization-time of flight mass spectroscopy), the compound exhibited M⁺(mass number of the corresponding cation formed by removal of 1electron) of 1051.2, thus confirming the objective iridium complex.

[0125] When the compound was dissolved in toluene and subjected tomeasurement of phosphorescence spectrum at an excited light wavelengthof 380 nm by using a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of620 nm, thus confirming clear red luminescence.

[0126] When the luminescence device prepared in Example 3 using theabove-synthesized metal coordination compound (Ex. Comp. No. 22) wassubjected to measurement of phosphorescence spectrum in a similarmanner, a clear red luminescence was confirmed similarly as in the caseof the compound in toluene described above.

EXAMPLE 9 Synthesis of Ex. Comp. No. 11

[0127] A metal coordination compound (Ex. Comp. No. 11) was synthesizedthrough the following reaction schemes. Hereinafter, the synthesis yieldis simply represented by “Y”.

[0128] According to MALDI-TOF MS, the compound exhibited M⁺=919.0, thusbeing identified as the objective iridium compound.

[0129] When the compound was dissolved in toluene and subjected tomeasurement of phosphorescence spectrum at an excited light wavelengthof 400 nm by using a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of612 nm, thus confirming clear red luminescence.

[0130] When a luminescence device having a layer structure shown belowand using the above-synthesized metal coordination compound (Ex. Comp.No. 11) was prepared and subjected to measurement of phosphorescencespectrum in a similar manner, a clear red luminescence was confirmedsimilarly as in the case of the compound in toluene described above.

[0131] ITO (100 nm)/α-NPD (40 nm)/CBP: Ex. Comp. No. 11 (95:5 byweight)(30 nm)/BCP (20 nm)/Alq3 (40 nm)/Al—Li (1 nm)/Al (100 nm).

[0132] Further, the luminescence device exhibited a good rectifyingcharacteristic.

[0133] Specifically, FIG. 3A is a graph showing a relationship betweenan electric field strength (E) and a current density of the luminescencedevice, and FIG. 3B is a graph showing a relationship between anelectric field strength (E) and a luminance (L) of the luminescencedevice. Further, FIG. 3C shows a luminescence spectrum of theluminescence device under application of a voltage of 10 volts.

[0134] The luminescence device exhibited a luminescence efficiency of0.8 lm/W under application of a voltage of 10 volts. The luminescencedevice also emitted stable luminescence even when the luminescencedevice was continuously supplied with the voltage for ca. 200 hours.

EXAMPLE 10 Synthesis of Ex. Comp. No. 45

[0135] A metal coordination compound (Ex. Comp. No. 45) was synthesizedthrough the following reaction schemes.

[0136] According to MALDI-TOF MS, the compound exhibited M⁺=1183.3, thusbeing identified as the objective iridium compound.

[0137] When the compound was dissolved in toluene and subjected tomeasurement of phosphorescence spectrum at an excited light wavelengthof 380 nm by using a fluorescence spectrometer, the compound exhibited aphosphorescence spectrum showing λmax (maximum emission wavelength) of603 nm, thus confirming clear reddish orange luminescence.

[0138] When the luminescence device prepared in Example 5 using theabove-synthesized metal coordination compound (Ex. Comp. No. 45) wassubjected to measurement of phosphorescence spectrum in a similarmanner, a clear reddish orange luminescence was confirmed similarly asin the case of the compound in toluene described above.

[0139] Further, the luminescence device exhibited a good rectifyingcharacteristic.

[0140] The luminescence device exhibited a luminescence efficiency of0.5 lm/W under application of a voltage of 8 volts. The luminescencedevice also emitted stable luminescence even when the luminescencedevice was continuously supplied with the voltage for ca. 150 hours.

EXAMPLE 11 Another Synthesis of Ex. Comp. No. 22

[0141] Tris[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N]iridium (III) (Ex.Comp. No. 22) prepared in Example 8 was synthesized through anotherreaction schemes shown below.

[0142] In a 200 ml-three-necked flask, 0.58 mg (1.64 mmole) of iridium(III) chloride-trihydrate (made by Across Organics Co.), 1.5 g (5.22mmole) of 2-(benzo[b]thienyl)-5-phenylpyridine, 45 ml of ethoxyethanoland 15 ml of water were placed and stirred for 30 min. at roomtemperature under nitrogen stream, followed by 24 hours of reflux understirring. The reaction product was cooled to room temperature, and theprecipitate was recovered by filtration and washed with water, followedsuccessive washing with ethanol and acetone. After drying under areduced pressure at room temperature, 1.02 g of red powderytetrakis[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N]-(μ-dichloro)diiridium(III) was obtained.

[0143] In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.95 g(0.72 mmole) of tetrakis[2-(benzo[b]thienyl)-5-phenylpyridine-C²N](μ-dichloro)-diiridium (III), 0.22 g (2.10 mM) of acetylacetone and1.04 g (9.91 mM) of sodium carbonate, were placed and stirred for 1 hourat room temperature under nitrogen stream and then refluxed understirring for 15 hours. The reaction product was cooled with ice, and theprecipitate was filtered out and washed with water. The precipitate wasthen purified by silica gel column chromatography (eluent:chloroform/methanol=30/1) to obtain 0.43 g of red powderybis[2-(benzo[b]thienyl)-5-phenylpyridine-C²,N](acetylacetonato)-iridium(III) (Example Compound No. 517). According to MALDI-TOF MS, M⁺ of 864.2of the compound was confirmed. A toluene solution of the compoundexhibited a luminescence spectrum showing λmax=631 nm and a quantumyield of 0.18 relative to 1.0 of Ir(ppy)₃.

[0144] In a 100 ml-three-necked flask, 0.27 g (0.94 mM) of2-(benzo[b]thienyl)-5-phenylpyridine, 0.36 g (0.42 mM) ofbis[2-benzo[b]thienyl)-5-phenylpyridine-C²,N](acetylacetonato)iridium(III) and 25 ml of glycerol, were placed and heated around 180° C. for 8hours under stirring and nitrogen stream. The reaction product wascooled to room temperature and poured into 170 ml of 1N-hydrochloricacid, and the precipitate was filtered out, washed with water and driedat 100° C. under a reduced pressure for 5 hours. The precipitate waspurified by silica gel column chromatography with chloroform as theeluent to obtain 0.27 g of red powderytris[2-(benzo[g]thienyl-5-phenylpyridine-C²,N]iridium (III) (ExampleCompound No. 22). According to MALDI-TOF MS, M⁺ of 1051.2 of thecompound was confirmed. A toluene solution of the compound exhibited aluminescence spectrum showing λmax=627 nm and a quantum yield of 0.17relative to 1.0 of Ir(ppy)₃.

[0145] The above-synthesized compound and a luminescence device preparedby using the compound exhibited luminescence characteristics similar tothose of the compound and luminescence device prepared in Example 8.

[0146] Bis[2-(benzo[g]thienyl)-5-phenylpyridine-C²,N]iridium (III) (Ex.Comp. No. 517) prepared in this example as an intermediate productexhibited λmax which was longer by ca. 4 nm than that of the finalproduct (Ex. Comp. No. 22) having three identical ligands. Further, whena luminescence device using the intermediate product was prepared andevaluated in the same manner as in Example 8, the luminescence deviceexhibited a luminescence spectrum showing λmax=631 nm. Accordingly, theintermediate product used in this example can also be used as aluminescence material.

EXAMPLE 12 Another Synthesis of Ex. Comp. No. 45

[0147] The metal coordination compound (Ex. Comp. No. 45) prepared inExample 10 was synthesized through another reaction schemes shown below.

[0148] In a 200 ml-three-necked flask, 0.58 mg (1.64 mmole) of iridium(III) chloride-trihydrate (made by Across Organics Co.), 1.7 g (5.1mmole) of a compound (1), 45 ml of ethoxyethanol and 15 ml of water wereplaced and stirred for 30 min. at room temperature under nitrogenstream, followed by 24 hours of reflux under stirring. The reactionproduct was cooled to room temperature, and the precipitate wasrecovered by filtration and washed with water, followed successivewashing with ethanol and acetone. After drying under a reduced pressureat room temperature, 1.0 g (yield=93.4%) of red powdery compound (2) wasobtained.

[0149] In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.90 g(0.71 mmole) of the compound (2), 0.22 g (2.10 mmole) of acetylacetoneand 1.04 g (9.91 mmole) of sodium carbonate, were placed and stirred for1 hour at room temperature under nitrogen stream and then refluxed understirring for 15 hours. The reaction product was cooled with ice, and theprecipitate was filtered out and washed with water. The precipitate wasthen purified by silica gel column chromatography (eluent:chloroform/methanol=30/1) to obtain 0.39 g of red powdery compound (3)(Example Compound No. 519). According to MALDI-TOF MS, M⁺ of 952.3 ofthe compound was confirmed. A toluene solution of the compound exhibiteda luminescence spectrum showing λmax=608 nm and a higher quantum yieldof 0.30 relative to 1.0 of Ir(ppy)₃ in this emission wavelength region.

[0150] In a 100 ml-three-necked flask, 0.29 g (0.88 mM) of the compound(1) 0.34 g (0.35 mM) of the compound (3) and 25 ml of glycerol, wereplaced and heated around 180° C. for 8 hours under stirring and nitrogenstream. The reaction product was cooled to room temperature and pouredinto 170 ml of 1N-hydrochloric acid, and the precipitate was filteredout, washed with water and dried at 100° C. under a reduced pressure for5 hours. The precipitate was purified by silica gel columnchromatography with chloroform as the eluent to obtain 0.23 g of redpowdery compound (4) (Example Compound No. 45). According to MALDI-TOFMS, M⁺ of 1183.4 of the compound was confirmed. A toluene solution ofthe compound exhibited a luminescence spectrum showing λmax=603 nm and aquantum yield of 0.278 relative to 1.0 of Ir(ppy)₃.

[0151] The above-synthesized compound and a luminescence device preparedby using the compound exhibited luminescence characteristics similar tothose of the compound and luminescence device prepared in Example 10.

[0152] The compound (3) (Ex. Comp. No. 519) prepared in this example asan intermediate product exhibited λmax which was longer by ca. 4 nm thanthat of the final product (Ex. Comp. No. 45) having three identicalligands. Further, when a luminescence device using the intermediateproduct was prepared and evaluated in the same manner as in Example 10,the luminescence device exhibited a luminescence spectrum showingλmax=608 nm and an external luminescence yield of 0.7 lm/W. Further, theluminescence device emitted stable luminescence even when continuouslysupplied with the voltage for ca. 100 hours. Accordingly, theintermediate product used in this example can also be used as aluminescence material.

EXAMPLE 13 Synthesis of Ex. Comp. Nos. 520 and 525

[0153] It is easy to synthesize the following compounds in the samemanner as in Example 11 except that 4-chloropyrimidine is synthesizedfrom 4(3H)-pyrimidone (made by Aldrich Co.) in the same manner as theprocess described at pages 37 and 38 of JP-A (Tokuhyo) 2001-504113(corr. to U.S. Pat. No. 6,300,330) and is reacted with 4-phenylboronicacid (made by Lancaster Co.) to obtain 4-(biphenyl-4-yl)pyrimidine,which is used instead of 2-(benzo[b]thienyl)-5-phenylpyridine.

[0154] Bis[4-(biphenyl-4-yl)pyridine-C^(3,)N³] (acetylacetonato) iridium(III) (Ex. Comp. No. 520).

[0155] Tris[4-(biphenyl-4-yl)pyrimidine-C³,N³] iridium (III) (Ex. Comp.No. 525).

EXAMPLE 14 Synthesis of Ex. Comp. Nos. 521 and 526

[0156] It is easy to synthesize the following compounds in the samemanner as in Example 11 except that 4-(4-chlorophenyl)pyrimidine issynthesized from 4-chloropyrimidine prepared in Example 13 and4-chlorophenylboronic acid (made by Aldrich Co.) and was reacted with2-naphthaleneboronic acid (made by Lancaster Co.) to obtain4-[4-(2-naphthyl)phenyl]-pyrimidine, which is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

[0157] Bis{4-[4-(2-naphthyl)phenyl]pyrimidine-C³,N³}(acetylacetonato)iridium (III) (Ex. Comp. No. 521).

[0158] Tris{4-[4-(2-naphthyl)phenyl]pyrimidine-C³,N³}iridium (III) (Ex.Comp. No. 526).

EXAMPLE 15 Synthesis of Ex. Comp. Nos. 522 and 527

[0159] It is easy to synthesize the following compounds in the samemanner as in Example 11 except that 2,4-diphenylpyridine is synthesizedfrom phenylboronic acid (made by Tokyo Kasei Kogyo K.K.) and4-phenyl-2-bromopyridine (made by General Intermediates of Canada) andwas used instead of 2-(benzo[b]thienyl)-5-phenylpyridine.

[0160] Bis(2,4-diphenylpyridine-C²,N¹)(acetylacetonato)iridium (III)(Ex. Comp. No. 522).

[0161] Tris(2,4-diphenylpyridine-C²,N¹)iridium (III) (Ex. Comp. No.527).

EXAMPLE 16 Synthesis of Ex. Comp. Nos. 523 and 528

[0162] It is easy to synthesize the following compounds in the samemanner as in Example 11 except that 2-(biphenyl-3-yl)pyridine issynthesized from 3-biphenylboronic acid (made by Lancaster Co.) and2-bromopyridine (made by Tokyo Kasei Kogyo K.K.) and is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

[0163] Bis[2-(biphenyl-3-yl)pyridine-C⁴,N³)(acetylacetonato)iridium(III) (Ex. Comp. No. 523).

[0164] Tris[2-(biphenyl-2-yl)pyridine-C⁴ ₁,N³)iridium (III) (Ex. Comp.No. 528).

EXAMPLE 17 Synthesis of Ex. Comp. Nos. 524 and 529

[0165] It is easy to synthesize the following compounds in the samemanner as in Example 11 except that 2-(5-bromothiophene-2-yl)pyridine issynthesized from 2-bromopyridine (made by Tokyo Kasei Kogyo K.K.) and5-bromothiophene-2-boronic acid (made by Aldrich Co.) and was reactedwith phenylboronic acid (made by Tokyo Kasei Kogyo K.K.) to obtain2-(5-phenylthiophene-2-yl)pyridine, which is used instead of2-(benzo[b]thienyl)-5-phenylpyridine.

[0166]Bis[2-(5-phenylthiophene-2-yl)pyridine-C²,N¹)(acetylacetonato)iridium(III) (Ex. Comp. No. 524).

[0167] Tris[2-(5-phenylthiophene-2-yl)pyridine-C²,N¹)iridium (III) (Ex.Comp. No. 529).

[0168] As described above, according to the present invention, the metalcoordination compound of the formula (1) characterized by aromaticsubstituent. The electroluminescence device (luminescence device) of thepresent invention using, as a luminescent center material, the metalcoordination compound of the formula (1) is an excellent device whichnot only allows high-efficiency luminescence but also retains a highluminance for a long period and shows little deterioration by currentpassage. Further, the display apparatus using the electroluminescencedevice of the present invention exhibits excellent display performances.

What is claimed is:
 1. A metal coordination compound represented byformula (1) below: ML_(m)L′_(n)  (1),wherein M is a metal atom of Ir,Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1,2 or 3 and n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partialstructure MLm is represented by formula (2) shown below and a partialstructure ML′_(n) is represented by formula (3) or (4) shown below:

wherein CyN1 and CyN2 are each cyclic group capable of having asubstituent, including a nitrogen atom and bonded to the metal atom Mvia the nitrogen atom; CyC1 and CyC2 are each cyclic group capable ofhaving a substituent, including a carbon atom and bonded to the metalatom M via the carbon atom with the proviso that the cyclic group CyN1and the cyclic group CyC1 are bonded to each other via a covalent bondand the cyclic group CyN2 and the cyclic group CyC2 are bonded to eachother via a covalent bond; the optional substituent of the cyclic groupsis selected from a halogen atom, cyano group, a nitro group, atrialkylsilyl group of which the alkyl groups are independently a linearor branched alkyl group having 1 to 8 carbon atoms, a linear or branchedalkyl group having 1 to 20 carbon atoms of which the alkyl group caninclude one or non-neighboring two or more methylene groups that can bereplaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and thealkyl group can include a hydrogen atom that can be optionally replacedwith a fluorine atom; or an aromatic group capable of having asubstituent which is selected from an aromatic group capable of having asubstituent (that is a halogen atom, a cyano atom, a nitro atom, alinear or branched alkyl group having 1 to 20 carbon atoms of which thealkyl group can include one or non-neighboring two or more methylenegroups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—or —C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom), a halogen atom, a cyano atom,a nitro atom, and a linear or branched alkyl group having 1 to 20 carbonatoms (of which the alkyl group can include one or non-neighboring twoor more methylene groups that can be replaced with —O—, —S—, —CO—,—CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include ahydrogen atom that can be optionally replaced with a fluorine atom); Eand G are independently a linear or branched alkyl group having 1 to 20carbon atoms of which the alkyl group can include a hydrogen atom thatcan be optionally replaced with a fluorine atom, or an aromatic groupcapable of having a substituent (that is a halogen atom, a cyano atom, anitro atom, a trialkylsilyl group of which the alkyl groups areindependently a linear or branched alkyl group having 1-8 carbon atoms,a linear or branched alkyl group having 1 to 20 carbon atoms of whichthe alkyl group can include one or non-neighboring two or more methylenegroups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH—or —C≡C—, and the alkyl group can include a hydrogen atom that can beoptionally replaced with a fluorine atom; and the cyclic groups CyN1,CyN2, CyC1 and CyC2 have at least one aromatic substituent capable ofhaving a substituent which is selected from an aromatic group capable ofhaving a substituent (that is a halogen atom, a cyano atom, a nitroatom, a linear or branched alkyl group having 1 to 20 carbon atoms ofwhich the alkyl group can include one or non-neighboring two or moremethylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—,—O—CO—, —CH═CH— or —C≡C—, and the alkyl group can include a hydrogenatom that can be optionally replaced with a fluorine atom), a halogenatom, a cyano atom, a nitro atom, a linear or branched alkyl grouphaving 1 to 20 carbon atoms of which the alkyl group can include one ornon-neighbouring two or more methylene groups that can be replaced with—O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, and the alkyl groupcan include a hydrogen atom that can be optionally replaced with afluorine atom).
 2. A metal coordination compound according to claim 1,including a partial structure ML′_(n) represented by the formula (3) inthe formula (1).
 3. A metal coordination compound according to claim 1,including a partial structure ML′_(n) represented by the formula (4) inthe formula (1).
 4. A metal coordination compound according to claim 1,wherein n is 0 in the formula (1).
 5. A metal coordination compoundaccording to claim 1, wherein in the formula (2), CyN1 is pyridyl groupand CyC1 is naphthyl group.
 6. A metal coordination compound accordingto claim 1, wherein in the formula (2), CyN1 is pyridyl group and CyC1is thienyl group.
 7. A metal coordination compound according to claim 1,wherein in the formula (2), CyN1 is pyridyl group and CyC1 isbenzothienyl group.
 8. An electroluminescence device, comprising: a pairof electrodes disposed on a substrate, and a luminescence unitcomprising at least one organic compound disposed between theelectrodes, wherein the organic compound comprises a metal coordinationcompound represented by the formula (1) in claim
 1. 9. A metalcoordination compound according to claim 8, including a partialstructure ML′_(n) represented by the formula (3) in the formula (1). 10.A metal coordination compound according to claim 8, including a partialstructure ML′_(n) represented by the formula (4) in the formula (1). 11.A metal coordination compound according to claim 8, wherein n is 0 inthe formula (1).
 12. An electroluminescence device according to claim 8,wherein a voltage is applied between the electrodes to emit light. 13.An electroluminescence device according to claim 8, wherein a voltage isapplied between the electrodes to emit phosphorescence.
 14. A picturedisplay apparatus, comprising an electroluminescence device according toclaim 8, and a means for supplying electric signals to theelectroluminescence device.